Use of crosslinked nitrogenous compounds which are soluble or dispersible in water in detergents and cleaners

ABSTRACT

The invention relates to the use of crosslinked nitrogenous compounds which are soluble or dispersible in water and are obtainable by crosslinking of 
     (a) compounds containing at least three NH groups with 
     (b) at least bifunctional crosslinkers which react with NH groups, 
     in detergents and cleaners, especially soil release agents. 
     Compounds (a) are preferably selected from the group consisting of oligo- and polyamines, polyalkylenepolyamines, polyamidoamines, polyamidoamines grafted with (poly)ethyleneimine, and mixtures thereof.

This application is a Division of application Ser. No. 09/500,534, filedon Feb. 9, 2000, abandoned, which is a divisional application of Ser.No. 09/284,456, filed May 12, 1999, (now U.S. Pat. No. 6,083,898, Issuedon Jul. 4, 2000), which was originally filed as InternationalApplication No. PCT/EP97/05744, filed Oct. 17, 1997.

The invention relates to the use of crosslinked nitrogenous compoundswhich are soluble or dispersible in water in detergents and cleaners.The invention particularly relates to the use of crosslinked oligo- andpolyamines as soil release agents and enzyme stabilizers in detergentsand cleaners.

The use of nitrogenous polymers in detergents is known.

DE-A1-31 24 210 describes liquid detergents with additives to preventdye transfer. The detergent additionally contains nonionic orzwitterionic surfactants in combination with polyethyleneimines,polyamines, polyamineamides or polyacrylamides, by which transfer ofdyes from colored textiles to white or pale-colored textiles on washingtogether is counteracted. The polyamineamides can be obtained bycondensing polybasic acids such as dibasic, saturated, aliphaticC₃₋₈-acids and polyamines. The polymers are described as soluble inwater but are not identified more exactly.

DE-A-1 922 450 describes detergents and cleaners which containantiredeposition agents to prevent reabsorption of detached soil on thecleaned surfaces. Polyamides which can be prepared frompolyethyleneimines with an average molecular weight of from 300 to 6000and di- and tricarboxylic acids are used as antiredeposition agents.Products of reactions with diglycolic acid, thiodiglycolic acid,iminodiacetic acid and nitrilotriacetic acid are also mentioned.

DE-A-2 165 900 describes detergents Smith a content of antiredepositionadditives The product of the reaction of a polyethyleneimine with amolecular weight of from 430 to 10,000 with C₈₋₁₈-alkyl glycidyl ethers,which may additionally be reacted with ethylene oxide is used asantiredeposition agent.

It is furthermore known to use soil release agents, which are reversiblyadsorbed from the wash liquor on the textile or the fibers of thetextile during the washing process, in detergents. When a textiletreated with such a soil release agent is soiled, in the next wash theadsorbed soil release agent improves detachment of the soil. This soilrelease effect is thus a reversible antisoil finish on the textileduring the washing. Various soil release agents are known such aspolyesters from polyethylene oxides with ethylene glycol and/orpropylene glycol and aromatic and/or aliphatic dicarboxylic adds. Forexample, DE-A-43 44 357 describes a soil release polymer which hasethylene glycol terephthalic groups and polyethylene glycol terephthalicgroups.

In addition, modified celluloses, such as methylcellulose,hydroxypropylcellulose or carboxymethylcellulose, have been employed.U.S. Pat. No. 4,138,352 describes the combination of a nonionic reactantand a hydroxybutylated methylcellulose with low molecular weight as soilrelease agent.

EP-A1-0 042 187 describes detergent compositions which contain smallamounts of substituted polyamines. The polyamines are in this casesubstituted by a longchain alkyl or alkenyl radical. They mayadditionally be substituted by at least two alkylene oxide residues ondifferent nitrogen atoms. The compositions show in particular improvedsoil release properties.

It is an object of the present invention to provide soil release agentsfor detergents and cleaners which preferably also act as enzymestabilizers and have an advantageous property profile.

We have found that this object is achieved by the use of crosslinkednitrogenous compounds which are soluble or dispersible in water and areobtainable by crosslinking of

(a) compounds containing at least three NH groups with

(b) at least bifunctional crosslinkers which react with NH groups,

in detergents and cleaners.

The NH groups can be present in primary (NH₂) and/or (NH) amino groups.

The nirogenous compounds according to the invention are preferably usedas soil release agents and/or enzyme stabilizers.

The soil release effect presumably derives from the adsorption,described above, of the agent from the wash liquor onto the textile. Thesoil release effect thus emerges on washing several times. It must bedistinguished from the single wash cycle or soil removal effect. Thesoil removal effect relates to detachment of soil directly on the firstwash of a stained, non-pretreated fabric. Polyamines ethoxylated withethylene oxide often show a single wash cycle or soil removal effect. Ithas been found, surprisingly, that oligo- and polyamines crosslinked inparticular by polyether chains show soil release properties. Theadditional enzyme-stabilizing effect was unexpected because thestabilizing additives employed to date have been mainly boric acidderivatives with polyols and alkyl- or arylboronic acids.

The compounds employed according to the invention moreover show theadvantageous properties in a large number of detergent formulations,such as heavy duty detergents, colored textile detergents, which can bein liquid or solid form.

Compounds (a)

The crosslinked nitrogenous compounds used according to the inventioncan be obtained by crosslinking of (a) compounds containing at leastthree NH groups. Compounds (a) are preferably selected from oligo- andpolyamines, polyalkylenepolyamines, polyamidoamines, polyamidoaminesgrafted with (poly)ethyleneimine, and mixtures thereofPolyallylenepolyamines are suitable as component (a).Polyalkylenepolyamines mean in the present connection compounds whichcontain at least three NH groups, eg. diethylene triamine,triethylenetetramine, tetraethylenepentamine, pentaethylenehexamine,diaminopropylethylenediamine, trisaminopropylamine andpolyethyleneimines. The polyethyleneimines preferably have an averagemolecular weight (Mw) of at least 300. The average molecular weight ofthe polyethyleneimines may be up to 1,000,000. Of particular interestindustrially is the use of polyethyleneimines with average molecularweights of from 600 to 25,000.

Also preferred are polyethyleneimine homopolymers with a degree ofpolymerization n of 5, 6, 10, 20, 35 and 100. Thesepolyethyleneiminehomopolymers may be prepared either water-containing oranhydrous, or be dehydrated. Synthesis of appropriate polyethyleneiminesis described in the examples.

The polyethyleneimines ray also be partly modified, for example in oneembodiment of the invention rendered hydrophobic with benzoic acid.

In one embodiment of the Invention, the polyalkylenepolyamine isselected from amines of the formula (I)

RR′N—[—(CR¹R²)_(x)—NR³—]_(a)—[—(CR⁴R⁶—]_(b)—R″  (I)

where the radicals R, R′ and R″, R¹, R², R⁴ and R⁵ are, independently ofone another, hydrogen atoms, linear or branched-chain C₁₋₂₀-alkyl-alkoxy, -hydroxyalkyl, -(alkyl)-carboxyl, -alcylamino radicals,C₂₋₂₀-alkenyl radicals or C₆₋₂₀-aryl, -aryloxy, -hydroxyaryl,-arylcarboxyl or -arylaino radicals, which may be further substituted,the radicals R³ and R⁶ are, independently of one another, hydrogenatoms, linear or branched-chain C₁₋₂₀-alkyl radicals, C₆₋₂₀-arylradicals, which are unsubstituted or substituted, or radicals[(CR⁷R⁸)₂—NR⁹]_(c)—R¹⁰, where the radicals R⁷, R⁸, R⁹ and R¹⁰ aredefined, independently of one another, as above for R, R′, R″, R¹, R²,R⁴, R⁵, or are carboxymethyl, carboxyethyl, phosphonomethyl orcarbamoylethyl radicals, x, y and z are, independently of one another,2, 3 or 4, and a, b and c are, independently of one another, integersfrom 0-300, there being at least three NH groups in the molecule.

5 to 100%, in particular 10 to 95%, of the nitrogen atoms in the aboveamines are preferably present in primary or secondary amino groups.

In one embodiment of the invention, the above amines have a numberaverage molecular weight of from 80 to 150,000, preferably 100 to50,000, particularly preferably 110 to 10,000, especially 129 to 5000.

The amine or polyalkylenepolyamine of the formula (I) may be a blockcopolymer or, in one embodiment of the invention, a polymer withrandomly distributed blocks or a polymer with an overall randomdistribution.

Further suitable compounds (a) are polyamidoamines. They are obtained,for example, by reacting dicarboxylic acids having 4 to 10 carbon atomswith polyalkylenepolyamines preferably containing 3 to 20 basic nitrogenatoms in the molecule. The reaction products should have at least threeNH groups. Examples of suitable dicarboxylic acids are succinic acid,maleic acid, adipic acid, glutaric acid, suberic acid, sebacic acid orterephthalic acid. Mixtures of carboxylic acids can also be employed,eg. mixtures of adipic acid and glutaric acid or maleic acid and adipicacid or technical dicarboxylic acid mixtures such as Sokolan® DCS fromBASF AG. Adipic acid or Sokolan® DCS is preferably used to prepare thepolyamidoamines. Suitable polyalkylenepolyamines condensed with thedicarboxylic acids have been mentioned above, eg. diethylenetriamine,triethylenetetramine, dipropylenetriamine, tripropylenetetramine,dihexamethylenetriamine, aminopropylethylenediamine andbisaminopropylethylenediamine. The polyalkylenepolyamines can also beemployed in the form of mixtures for preparing the polyamidoamines. Thepolyamidoamines are preferably prepared without diluent, but this canalso take place in inert solvents where appropriate. The dicarboxylicacids are condensed with the polyalkylenepolyamines at elevatedtemperatures, eg. in the range from 100 to 220° C. The water formed inthe reaction is distilled out of the reaction mixture. The condensationcan, where appropriate, also be carried out in the presence of lactonesor lactams of carboxylic acids having 4 to 8 carbon atoms. From 0.8 to1.4 mol of a polyalkylenepolyamine are normally used per mole ofdicarboxylic acid. The polyamidoamines obtainable in this way haveprimary and secondary amino groups, contain tertiary nitrogen atoms andare soluble in water.

Also suitable as component (a) are polyamidoamines grafted withethyleneimine. Products of this type can be prepared by allowingethyleneimine to act on the poly-amidoamines described above in thepresence of acids or Lewis acids, eg. sulfuric acid, phosphoric acid orboron trifluoride etherate. Ethyleneimine is grafted onto thepolyamidoamine under the conditions described. It is possible, forexample, to graft from 1 to 20 ethyleneimine units on for each basicnitrogen group in the polyamidoamine, ie. about 10-1000, preferably3-500, parts by weight of ethyleneimine are employed per 100 parts byweight of a polyamidoamine.

The polyalkylenepolyamines described above may be partially amidated.Products of this type are prepared, for example, by reactingpolyalkylenepolyamines with mono-carboxylic acids or esters of monobasiccarboxylic acids and monohydric C₁-C₄-alcohols. Thepolyalkylenepolyamines are preferably 1-30, usually only up to 20%,amidated for the subsequent reactions. The amidatedpolyalkylenepolyamines must still have at least three free NH groups sothat they can be reacted with the crosslinkers (b). Monocarboxylic acidshaving 1 to 28 carbon atoms can be employed for amidating thepolyalkylenepolyamines for example. Examples of suitable carboxylicacids are formic acid, acetic acid, propionic acid, benzoic acid,salicylic acid, lauric acid, palmitic acid, stearic acid, oleic acid,linoleic acid and behenic acid, and naturally occurring mixtures offatty acids such as coconut fatty acid. Amidation can be carried out,for example, by reacting the polyalkylenepolyamines with alkyldiketenes.

The polyalkylenepolyamines can also be used in partially quaternizedform as compounds of group (a). Examples of suitable quaterning agentsare alkyl halides such as methyl chloride, ethyl chloride, butylchloride, epichlorohydrin, hexyl chloride and benzyl chloride, anddimethyl sulfate and diethyl sulfate. If quaternized polyalkylenepolyamines are employed as compound of group (a), the degree ofquaternization is preferably 1 to 30, normally only up to 20% so thatsufficient free NH groups are available for reaction with thecrosslinker (b).

Compounds of group (a) which are preferably used are polyethyleneimineswith an average molecular weight of from 300 to 25,000, preferably 300to 3000, and poly-amidoamines grafted with ethyleneimine.

It is likewise possible to use according to the invention polymers (a)which contain repeating units of the following formula:

—[CH₂—CH(NH₂)]—

These mean, in particular, oligo/polyvinylformamides and copolymers ofvinylformamide in which the formamide groups are at least partly,preferably 5-100 mol %, convened into amino groups by hydrolysis.Oligo/polyvinylformamides in which the formamide groups have been 20-100mol %, in particular 40-100 mol %, convened into amino groups byhydrolysis are preferably employed. The hydrolysis can be carried outeither in alkaline or in acidic medium.

In one embodiment of the invention, these polymers have a number averagemolecular weight of from 80 to 150,000, preferably 100 to 50,000,particularly preferably 110 to 10,000, especially 129 to 5000.

The amines or polyamines used according to the invention are prepared byknown processes.

In one embodiment of the invention, component (a) is selected fromamines of the formula (II)

(R¹R¹)N—X—N(R¹R¹)  (II)

where the radicals R¹ are hydrogen atoms or (R²R²)N(CH)² _(n)— radicals,

the radicals R² are hydrogen atoms or (R³R³)N—(CH₂)_(n)— radicals,

the radicals R³ are hydrogen atoms or (R⁴R⁴)N—(CH₂)_(n)— radicals,

the radicals R⁴ are hydrogen atoms or (R⁵R⁵)N—(CH₂)_(n)— radicals,

the radicals R⁵ are hydrogen atoms or (R⁶R⁶)N—(CH₂)_(n)— radicals,

the radicals R⁶ are hydrogen atoms, n is 2, 3 or 4, and the radical X isone of the radicals

—(CH₂)_(p)—, —CH₂)₃—NR¹¹—(CH₂)₃—,—(CH₂)₁—[O—(CH₂)_(k)]_(m)—O—(CH₂)₁—C₂₋₂₀-akylene,

the radical Y is an oxygen atom, a CR⁷R⁹C═O or SO₂ radical,

p is an integer from 2-20,

l and k are, independently of one another, an integer from 2-6,

m is an integer from 1-40,

the radicals R⁷, R⁸, R⁹ and R¹⁰ are, independently of one another,hydrogen atoms or C₁₋₆-alkyl radicals,

and the radical R¹¹ is C₁₋₂₀-alkyl, C₂₋₂₀-dialkylamino-C₂₋₁₀-alkyl,C₁₋₁₀-alkoxy-C₂₋₁₀-alkyl, C₂₋₂₀-hydroxyalkyl, C₃₋₁₂-cycloalkyl,C₄₋₂₀-cycloalkylalkyl, C₂₋₂₀-alkenyl, C₄₋₃₀-dialkylaminoalkenyl,C₃₋₃₀-alkoxyalkenyl, C₃₋₂₀-hydroxyalkenyl, C₅₋₂₀-cycloalkylalkenyl, anaryl or a C₇₋₂₀-arylalkyl radical which is unsubstituted or substitutedone to five times by C₁₋₈-alkyl, C₂₋₈-dialkylamino, C₁₋₈-alkoxy,hydroxyl, C₃₋₈-cycloalkyl and/or C₄₋₁₂-cycloalkylalkyl, or two radicalsR¹¹ together form an alkylene chain which may be interrupted by nitrogenor oxygen, such as from ethylene oxide, propylene oxide, butylene oxideand —CH₂—CH(CH₃)—O— or polyisobutylene with 1 to 100 isobutylene units,

where 5-100% of the nitrogen atoms are in primary or secondary aminogroups.

The radicals R⁷, R⁸, R⁹, R¹⁰ in the formula II are C₁₋₆-alkyl radicals,preferably C₁₋₃-alkyl radicals, such as methyl, ethyl, n-propyl andisopropyl radicals, particularly preferably methyl and ethyl radicals,especially methyl radicals, or preferably hydrogen, with the radicals R⁷and R⁸, and R⁹ and R¹⁰, preferably being identical.

Examples of radicals R¹¹ according to the invention are C₁₋₂₀-alkylradicals, preferably C₁₋₁₂-alkyl radicals such as methyl, ethyl,n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, n-pentyl,isopentyl, sec-pentyl, neopentyl, 1,2-dimethylpropyl, n-hexyl, isohexyl,sec-hexyl, n-heptyl isoheptyl, n-octyl isooctyl, n-nonyl, isononyl,n-decyl, isodecyl, n-undecyl, isoundecyl, n-dodecyl and isododecylradicals, particularly preferably C₁₋₄-alkyl radicals such as methyl,ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl and tert-butylradicals, aryl radicals such as phenyl, 1-naphthyl and 2-naphthylradicals, preferably phenyl radicals, C₇₋₂₀-aryl radicals, preferablyC₇₋₁₂-phenylalkyl radicals, such as benzyl, 1-phenethyl, 2-phenethyl,1-phenylpropyl, 2-phenylpropyl, 3-phenylpropyl, 1-phenylbutyl,2-phenylbutyl, 3-phenylbutyl and 4-phenylbutyl radicals, particularlypreferably benzyl 1-phenethyl and 2-phenethyl radicals, C₇₋₂₀-alkylarylradicals, preferably C₇₋₁₂-alkylphenyl radicals such as 2-methylphenyl,3-methylphenyl 4-methylphenyl, 2,4-dimethylphenyl, 2,5-dimethylphenyl,2,6-dimethylphenyl, 3,4-dimethylphenyl, 3,5-methylphenyl,2,3,4-trimethylphenyl, 2,3,5-trimethylphenyl, 2,3,6-trimethylphenyl,2,4,6-trimethylphenyl, 2-ethylphenyl, 3-ethylphenyl, 4-ethylphenyl,2-i-propylphenyl, 3-n-propylphenyl and 4-n-propylphenyl radicals orpolyisobutylene radicals with 1-100, preferably 1-70, particularlypreferably 1-50, isobutylene units.

The amines of the formula (II) are preferably prepared by the processdescribed in WO 96/15097.

They are preferably prepared from diamines of the formulaNH₂—(CH₂)_(n)—NH₂ where n is an integer from 2 to 20. Examples ofsuitable diamines of this type are 1,2-ethylene-diamine,1,3-propylenediamine, 1,4-butylenediamine and 1,6-hexamethylenediamine.Primary tetraaminoalkylalkylenediamines are likewise preferablyemployed, such as N,N,N′,N′-tetraaminopropyl-1,2-ethylenediamine,N,N,N′,N′-tetraminopropyl-1,3-propylerediamine,N,N,N′,N′-tetraaminopropyl-1,4-butylenediamine andN,N,N′,N′-tetraaminopropyl-1,6-hexamethylenediamine.

Preferred examples of amines (II) according to the invention, which arealso referred to as dendrimeric amines, and their precursors, areN,N,N′,N′-tetraamino-propylethylenediamine, refereed to as N6-aminehereinafter, and the dendrimeric amines which can be prepared therefromby aminopropylation and are referred to by the number of their nitrogenatoms, such as N14, N30, N62 and N126 amine from BASF AG. These amineshave a basic ethylenediamine framework in which the hydrogen atoms onthe nitrogen are replaced by amino(n-propyl)radicals. The terminal aminogroups may in turn be substituted by corresponding aminopropyl groups(N14 amine) etc. Processes for preparing these amines are described inWO 96/15097, starting from ethylenediamine. Likewise preferred examplesof these amines according to the invention are corresponding N amines asdescribed in WO 93/14147, which are prepared starting frombutylenediamine instead of ethylenediamine as above. Amines of this typeare prepared and marketed by DsM N.V. in the Netherlands.

Further components (a) which are preferred according to the inventionare polyamines of the following formula

RR′N—[—(CH₂)_(m)—NR″]_(x)—R′″

where the radicals R, R′ or R″ are, independently of one another,hydrogen atoms, C₁₋₁₀-alkyl radicals, C₂₋₂₀-alkenyl radicals orC₆₋₂₀-aryl radicals,

the radical R′″ is a hydrogen atom or a—(CH₂)_(o)—[NH—(CH₂)_(m)—]_(p)—NH₂ radical or a hydroxyalkyl or alkoxyradical, where x is an integer from 1-10,

m is an integer from 2-4,

o is an integer from 2-4, and

p is an integer from 0-10.

Particularly preferred amines are those of the following formula

H₂N—[—(CH₂)_(m)NH0]_(x)—H

where m is 2, 3 or 4 and x is an integer from 1-10,

RR′N—[—CH₂)_(m)—NH]_(x)—H

where the radicals R and R′ are, independently of one anotherC₁₋₂₀-alkyl radicals, C₂₋₂₀-alkenyl radicals or C₆₋₂₀-aryl radicals,

mis 2, 3 or 4, and

x is an integer from 1-10,

H₂N—(CH₂)₄—NR—(CH₂)₄—NH₂

where the radical R is a hydrogen atom or a C₁₋₂₀-alkyl radical,C₂₋₂₀-alkenyl radical or C₆₋₂₀-aryl radical,

H₂N—[—(CH₂)_(m)NH]_(x)—(CH₂)_(o)—[NH—(CH₂)_(m)—]_(p)NH₂

where m is 2, 3 or 4,

o is 2, 3 or 4,

x is an integer from 0-10,

p is an integer from 0-10, and

the total of x and p is ≧1.

Preferred compounds (a) areN,N,N′,N′-tetraaminopropyl-1,2-ethylenediamine or polyethyleneimine witha degree of polymerization of from 5 to 500, preferably from 5 to 50.

Crosslinkers (b)

The nitrogenous compounds described above are reacted with at least oneat least bifunctional crosslinker which reacts with NH groups to givecrosslinked nitrogenous compounds which are soluble or dispersible inwater. Crosslinkers (b) are preferably selected from the groupconsisting of the halogen-free crosslinkers

(1) polyepoxides

(2) ethylene carbonate, propylene carbonate and/or urea,

(3) monoethylenically unsaturated carboxylic acids and their esters,amides and anhydrides, at least dibasic carboxylic acids orpolycarboxylic acids, and their esters, amides and anhydrides,

(4) products of the reaction of polyetherdiamines, alkylenediamines,polyalkylene-polyamines, bifunctional or multifunctional alcohols,alkylene glycols, polyalkylene glycols, functionalized polyesters orpolyamides or their mixtures with monoethylenically unsaturatedcarboxylic acids or their esters, amides or anhydrides, the reactionproducts having at least two ethylenic double bonds, carboxaride,carboxyl or ester groups as functional groups,

(5) products, containing at least two aziridino groups, of the reactionof dicarboxylic esters with ethyleneimine,

(6) cumulenes and polyheterocumulenes,

(7) β-keto esters, β-keto acids and β-keto aldehydes,

(8) functionalized glycidyl ethers, the halogen-containing crosslinkers

(9) polyhalides

(10) glycidyl halides,

(11) chloroformates and chloroacetic acid derivatives,

(12) epichlorohydrin, glycerol chlorohydrin, polyether dichlorohydrincompounds,

(13) phosgene or mixtures thereof.

Examples of polyepoxides (1) are polyalkylene glycol bisglycidyl etherswhich are prepared from bischlorohydrins such as bischlorohydrins ofpolyethylene glycols under alkaline conditions. The alkylene glycolspreferably have 2 to 10 carbon atoms, and are, in particular, ethyleneglycol, 1-methylethylene glycol or 1-ethylethylene glycol.

It is likewise possible to use alkanediol bisglycidyl ethers, preferablyof a C₂₋₁₂-alkanediol which is, in particular, linear. Examples arebutanediol bisglycidyl ether and hexanediol bisglycidyl ether.

It is additionally possible to use aryl bisglycidyl ethers and cyclicalkyl bisglycidyl ethers which are derived, in particular, from benzenenuclei or dimethylcyclohexane nuclei, which may in turn be substituted.It is likewise possible to use bisepoxides such as bis-ethylene oxideand ethylene oxide units which are separated by a linear C₁₋₁₂-alkyleneradical.

Preferably employed from group (2), ethylene carbonate, propylenecarbonate and/or urea, is propylene carbonate.

Monoethylenically unsaturated carboxylic acids and their esters, amidesand anhydrides from group (3) are, for example, acrylic acid,methacrylic acid, crotonic acid, acrylates or acrylamides from primaryor secondary amines. The alcohol residue has in this case 1 to 22,preferably 1 to 18, carbon atoms, and the amine residue 0 to 12 carbonatoms. At least dibasic carboxylic acids or polycarboxylic acids can beeither saturated or unsaturated. Examples are tartaric acid and itsanalogs, and C₂₋₅₀-dicarboxylic acids, in particular linearC₂₋₂₀-alkylenedicarboxylic acids, and their esters, amides oranhydrides. Esters or diesters can be formed with C₁₋₂₂-alcohols, andamides and diamides may have C₁₋₂₂ radicals.

Examples of suitable dicarboxylic esters are dimethyl oxalate, diethyloxalate, diisopropyl oxalate, dimethyl succinate, diethyl succinate,diisopropyl succinate, di-n-propyl succinate, diisobutyl succinate,dimethyl adipate, diethyl adipate and diisopropyl adipate.

Examples of unsaturated acids are maleic acid, itaconic acid and theiranhydrides or esters.

Examples of polycarboxylic acids are citric acid, propanetricarboxylicacid, ethylenediaminetetraacetic acid, butanetetracarboxylic acid, andhiger polycarboxylic acids. It is also possible to use polymers ofmethacrylic acid, maleic acid, itaconic acid or mixtures thereof It isalso possible to employ copolymers with C₂₋₃₀-olefins, such ascopolymers of maleic anhydride and isobutene or diisobutene. Theanhydride groups may moreover be converted into esters or amides.Examples of suitable polymers are described in EP-A 0 276 464, U.S. Pat.No. 3,810,834, GB-A 1 411 063 and U.S. Pat. No. 4,818,795.

It is furthermore possible to employ salts of all the acids mentioned.

Examples of group (4) are polyetherdiacrylic acid, -diacrylic esters and-diacrylamides, for example compounds which have 1 to 50 ethylene oxideunits and in which the alcohol residue in the ester has 1 to 22 carbonatoms, and the amides which can be formed from ammonia, primary orsecondary amines with C₁₋₂₂ radicals. Other examples areethylenediaminediacrylates and polyetherdiaminediacrylates. The alcoholresidues in the acrylates once again have 1 to 22 carbon atoms, and thepolyether portion can have 0 to 50 repeating units. Apart from ethyleneoxide units, the polyether block can also be composed of propylene oxideunits or THF units. One example is a poly-THF-diaminediacrylate or-acrylamide or acrylic acid. The amine functionalities may also bederived from the amines mentioned at the outset.

The acrylate groups are in this case bonded to the amine groups byMichael addition. They may also be linked by amide formation with theamine groups of the polyether diamines, so that the molecules have twoethylenically unsaturated groups. Poly-THF-diacrylamides can be usedcorrespondingly. It is furthermore possible to use polyiminedi- and-polyacrylates in which two or more NH groups are added onto acrylatesby Michael additions. It is possible to use correspondinglypolyaminediacrylates and polyimine-MA-monoamides orpolyamine-MA-monoamides. In these cases, the terminal amino groups inthe polymine or polyamine are in each case reacted with one molecule ofmaleic anhydride (MA) to give the corresponding monoamides. Theremaining acid functionalities in the maleic acid can in this case bereplaced by esters or amides. It is likewise possible to use a polyetherdiamine dimaleic monoamide, ie. a polyetherdiamine whose two terminalamino groups have each been reacted with one maleic anhydride moleculeto give an amide. The remaining acid functionalities of the maleicanhydride may likewise be in the form of esters or amides. The polyetherdiamines, polyimines or polyamines preferably have 5 to 50 repeatingunits.

The resulting products should in general have at least two ethylenicdouble bonds, carboxamide, carboxyl or ester groups as functionalgroups. Products of the reactions of amines or glycols with maleicanhydride, such as alkylene glycols, polyethylene glycols,polyethyleneimines or polypropyleneimines preferably have molecularweights in the range from 400 to 100,000. Products of the reaction ofmaleic anhydride with α,ω)-polyethyleneimines with a molecular weight offrom 400 to 5000, products of the reaction of polyethyleneimines with amolecular weight of from 129 to 50,000 with maleic anhydride, andproducts of the reaction of ethylenediamine or triethylenetetramine withmaleic anhydride in the molar ratio not exceeding 1:2 are particularlypreferred. The polyetherdiamines, alkylenediamines andpolyalkylenepolyamines can also be reacted with maleic anhydride in aMichael addition.

Examples of compounds of group (5) are products of the reaction ofC₂₋₅₀-dicarboxylic acids, especially linear alkylenedicarboxylic acids,with ethyleneimine. One example is α-1-aziridinoethyloxamide.

Examples of cumulenes and polyheterocumulenes of group (6) are2,6-tolylene diisocyanate, 2,4-tolylene diisocyanate and compounds ofthe formulae O═C═N—X—N═C⊚O and S═C═N—X—N═C═S, where X is aC₁₋₂₂-alkylene radical or C₆₋₂₀-arylene radical.

β-Keto esters, β-keto acids and β-keto aldehydes (7) may have theformula R¹—C(=O) CR²R³—C(═O)—R⁴ where the radicals R¹ to R³ can behydrogen atoms or C₁₋₁₂-alkyl radicals, and R′ can be hydrogen, OH or aC₁₋₂₂-alkoxy radical.

Examples of functionalized glycidyl ethers (8) are glycidyl acrylate or2-propenyl glycidyl ether

Examples of halogen-containing crosslinkers are polyhalides (9) such aslinear C₁₋₁₀-alkylene dichlorides, such as dichloromethane or1,2-dichloromethane. The polyhalides may also be derived frompolyethylene oxides or ethylene oxides substituted by methyl or ethylradicals. They may likewise be present in poly-THF molecules, in whichcase the halides are at the ends of the polymer chain. It is moreoverpossible to use random polymers or block copolymers of correspondingpolyethers which have two halogen atoms. The weight average molecularweight is preferably 300 to 3000.

Glycidyl halides (10) which can be used are epichlorohydrin and glycidylethers of haloalkanes or aromatic halogen compounds. The halogen atomsof the crosslinkers (9) and (10) and of the following crosslinkers arepreferably chlorine atoms or bromine atoms, in particular chlorineatoms.

Glycerol chlorohydrin and polyether dichlorohydrin compounds (12) areprepared from epichlorohydrin and the appropriate alcohols, ie. glycerolor polyethylene glycols. The polymeric crosslinkers generally have aweight average molecular weight of from 100 to 10,000, preferably 300 to3000. Particularly preferred crosslinkers are bischlorohydrins andbiselycidyl ethers of polyethylene glycols. The bisglycidyl ethers canbe prepared under alkaline conditions.

Preparation of the Crosslinked Nitrogenous Compounds

The water-soluble reaction products according to the invention can beobtained by reacting the compounds of components (a) with thecrosslinkers of component (b). The reaction is preferably carried out inaqueous medium. Condensation of components (a) and (b) is carried out,for example, at a temperature in the range from 0 to 200° C., preferably20 to 160° C. If the condensation is carried out in an aqueous solutionat temperatures above the boiling point of water, the reaction isundertaken in press tight apparatus. However, the condensation can alsobe carried out without diluent or in solvents which are inert to thereactants, such as high-boiling ethers (diethylene glycol dimethylether), tetrahydrofuran, polyols, toluene, xylens, other high-boilingsubstituted aromatic compounds or commercial hydrocarbon fractionsboiling in the range from 50 to 300° C. In the case of condensation inaqueous solution, the pH of the reaction mixture is, for example, 2 to12, preferably 5 to 11. In most cases, condensation is carried out atthe pH set up when the reactants dissolve in the water. Theconcentration of the resulting water-soluble condensates in the aqueoussolution is, for example, 10 to 90% by weight and is preferably in therange from 20 to 80% by weight. The reaction products are regarded assoluble in water when they are able to form a solution with a strengthof at least 5% by weight in water at room temperature. Condensation ofthe compounds of components (a) and (b) is preferably carried out inaqueous solution so as to result in water-soluble condensates which, ina 20% by weight aqueous solution at 20° C., have a viscosity of at least100 mPas, preferably 100 to 15,000 mPas (measured at pH 7 in aBrookfield viscometer).

The mixtures reacted in the condensation contain from 50 to 99.9% byweight, preferably 60 to 99.5% by weight, of at least one compound ofcomponent (a) and from 0.1 to 50% by weight, preferably 0.5 to 40% byweight, of at least one compound of component (b), with the total ofcomponents (a) and (b) always being 100% by weight.

The result, especially when oligoamines or polyamines andbisfunctionalized polyethylene glycol blocks are used, is, depending onthe reaction conditions and molar ratio, a polymer with a networkstructure consisting of amine and polyethylene glycol blocks of definedsize, chain length and molecular weight distribution. The compoundsaccording to the invention improve the detachment of soil in the washingof textiles on the one hand due to the soil release properties, and onthe other hand due to the enzyme-stabilizing effect, which increases theactivity of the enzymes. Enzymes present in modern detergents, such asproteases, lipases, cellulases, amylases and peroxidases, which are usedto improve the detergency performance, are exposed to destabilizing andinactivating conditions in the detergent formulation. These conditionsmay be caused by various ingredients in the formulation, such as thesuit system, the bleach system, the alkalis etc. This problem is commonin liquid detergent formulations in particular, because the enzymes arenot protected from contact owing to the mobility of the detergentingredients. In this case, the crosslinked compounds according to theinvention result in a stabilization and retention of the enzymes, whichare thus able to display their full effect in the washing process.

Addition of even small amounts of the crosslinked nitrogenous compoundsaccording to the invention, especially the crosslinked polyamines,improves the soil-releasing properties of color detergent, heavy dutydetergent or compact detergent formulations. The compounds according tothe invention are probably adsorbed from the wash liquor onto thetextiles. When a textile treated in this way is soiled, the compoundsapplied to the textile result in a distinctly improved detachment ofsoil in the subsequent wash. The compounds according to the inventionare particularly effective for stains consisting of a combination offatty or oily soil and pigment particles, for example stains consistingof used engine oil, lipstick, makeup or shoe cream. The compounds areparticularly advantageous for cleaning polyester fabrics orpolyester-containing fabrics.

The invention thus also relates to detergents and cleaners comprising atleast one crosslinked nitrogenous compound as defined above, and atleast one surfactant. The detergent and cleaner preferably comprises atleast one enzyme in addition.

These detergents can be used according to the invention for washingtextiles.

The detergents according to the invention may furthermore comprise theingredients conventionally used in detergents, such as builders,surfactants, bleaches, enzymes and other ingredients as describedhereinafter.

Builders

Inorganic builders (A) suitable for combination with the(polyalkylenepoly)amines according to the invention are, in particular,crystalline or amorphous aluminosilicates with ion-exchanging propertiessuch as, in particular, zeolites. Various types of zeolites aresuitable, in particular zeolites A, X, B, P, MAP and HS in their Na formor in forms in which Na is partly replaced by other cations such as Li,Ca, Mg or ammonium. Suitable zeolites are described, for example, inEP-A 038591, EP-A 021491, EP-A 087035, US-A 4604224, GB-A 2013259, EP-A522726, EP-A 384070 and WO-A 94/24251.

Examples of suitable crystalline silicates (A) are disilicates or sheetsilicates, eg. SKS-6 (manufactured by Hoechst AG). The silicates can beemployed in the form of their alkali metal, alkaline earth metal orammonium salts, preferably as Na, Li and Mg silicates.

Amorphous silicates such as sodium metasilicate with a polymericstructure, or Britesil® (manufactured by Akzo N.V. in the Netherlands)can likewise be used. Suitable carbonate-based inorganic builders arecarbonates and bicarbonates. These can be employed in the form of theiralkali metal, alkaline earth metal or ammonium salts.

Na, Li and Me carbonates and bicarbonates, especially sodium carbonateand/or sodium bicarbonate, are preferably employed.

Phosphates usual as inorganic builders are polyphosphates, eg.pentasodium triphosphate.

Said components (A) can be employed singly or in mixtures with oneanother. An inorganic builder component of particular interest is amixture of aluminosilicates and carbonates, especially of zeolites, inparticular zeolite A, and alkali metal carbonates, in particular sodiumcarbonate, in the ratio of from 98:2 to 20:80, in particular from 85:15to 40:60, by weight. Other components (A) may also be present inaddition to this mixture.

In a preferred embodiment, the textile detergent formulation accordingto the invention contains 0.1 to 20% by weight, in particular 1 to 12%by weight, of organic cobuilders (B) in the form of low molecular weightoligomeric or polymeric carboxylic acids, especially polycarboxylicacids, or phosphonic acids or their salts, in particular Na or K salts.

Examples of suitable low molecular weight carboxylic acids or phosphonicacids for (B) are:

C₄-C₂₀-di-, -tri- and -tetracarboxylic acids such as succinic acid,propanetricarboxylic acid, butanetetracarboxylic acid,cyclopentanetetracarboxylic acid and alkyl- and alkenylsuccinic acidswith C₂-C₁₆-alkyl and -alkenyl radicals respectively;

C₄-C₂₀-hydroxy carboxylic acids such as malic acid, tartaric acid,gluconic acid, glutaric acid, citric acid, lactobionic acid andsucrosemono-, -di- and -tricarboxylic acids;

aminopolycarboxylic acids such as nitilotriacetic acid,β-alaminediacetic acid, ethylenediaminetetraacetic acid, serinediaceticacid, isoserinediacetic acid, methyl-glycinediacetic acid andalkylethylenediaminetriacetates;

salts of phosphonic acids such as hydroxyethanediphosphonic acid.

Examples of suitable oligomeric or polymeric carboxylic acids for (B)are:

Oligomaleic acids as described, for example, in EP-A 0 451 508 and EP-A0 396 303;

co- and terpolymers of unsaturated C₄-C₈-dicarboxylic acids, possiblecomonomers being monoethylenicaly unsaturated monomers

from group (i) in amounts of up to 95% by weight,

from group (ii) in amounts of up to 60% by weight and from group (iii)in amounts of up to 20% by weight.

Examples of suitable unsaturated C₄-C₈-dicarboxylic acids in this caseare maleic acid, fumaric acid, itaconic acid and citraconic acid. Maleicacid is preferred.

Group (i) comprises monoethylenically unsaturated C₃-C₈-monocarboxylicacids such as acrylic acid, methacrylic acid, crotonic acid andvinylacefic acid. Preferably employed from group (i) are acrylic acidand methacrylic acid.

Group (ii) comprises monoethylenically unsaturated C₂-C₂₂-olefins, vinylalkyl ethers with C₁-C₈-alkyl groups, styrene, vinyl esters ofC₁-C₈-carboxylic acids, (meth)-acrylamide and vinylpyrrolidone.Preferably employed from group (ii) are C₂-C₆-olefins, vinyl alkylethers with C₁-C₄-alkyl groups, vinyl acetate and vinyl propionate.

Group (iii) comprises (meth)acrylic esters of C₁-C₈-alcohols,(meth)acrylonitrile, (methacrylamides of C₁-C₈-amines, N-vinylformamideand vinylimidazole.

If the group (ii) polymers contain vinyl ester units, these can also bepartly or completely hydrolyzed to vinyl alcohol structural units.Suitable co- and terpolymers are disclosed, for example, in U.S. Pat.No. 3,887,806 and DE-A 43 13 909.

Suitable and preferred copolymers of dicarboxylic acids for component(B) are:

copolymers of maleic acid and acetic acid in the ratio 100:90 to 95:5 byweight, particularly preferably those in the ratio 30:70 to 90:10 byweight, with molecular weights of from 100,000 to 150,000:

terpolymers of maleic acid, acrylic acid and a vinyl ester of aC₁-C₃-carboxylic acid in the ratio 10 (maleic acid):90 (acrylicacid+vinyl ester) to 95 (maleic acid):10 (acrylic acid+vinyl ester) byweight, it being possible for the ratio of acrylic acid to the vinylester to vary in the range from 30:70 to 70:30 by weight;

copolymers of maleic acid with C₂-C₈-olefins in the molar ratio 40:60 to80:20, with copolymers of maleic acid with ethylene, propylene orisobutylene in the molar ratio 50:50 being particularly preferred.

Graft copolymers of unsaturated carboxylic acids on low molecular weightcarbohydrates or hydrogenated carbohydrates, cf. U.S. Pat. No.5,227,446, DE-A 44 15 623 and DE-A 43 13 909, are likewise suitable ascomponent (B).

Examples of suitable unsaturated carboxylic acids in this case aremaleic acid, fumaric acid, itaconic acid, citraconic acid, acrylic acid,methacrylic acid, crotonic acid and vinylacetic acid, and mixtures ofacrylic acid and maleic acid, which are grafted on in amounts of from 40to 95% of the weight of the component to be grafted.

It is additionally possible for up to 30% by weight, based on thecomponent to be grafted, of other monoethylenically unsaturated monomerunits to be present in the polymer for modification. Suitable modifyingmonomers are the abovementioned monomers of groups (ii) and (iii).

Suitable as grafting base are degraded polysaccharides such asacidically or enzymatically degraded starches, inulins or cellulose,protein hydrolysates and reduced (hydrogenated or reductively aminated)degraded polysaccharides such as mannitol, sorbitol, aminosorbitol andN-alkylglucamine, and polyalkylene glycols with molecular weights of upto Mw=5000, such as polyethylene glycols, ethylene oxide/propylene oxideor ethylene oxidelbutylene oxide or ethylene oxide/propyleneoxidelbutylene oxide block copolymers and alkoxylated monohydric orpolyhydric C₁-C₂₂-alcohols, cf. U.S. Pat. No. 5,756,456.

Preferably employed from this group are strayed degraded or degradedreduced starches and grafted polyethylene oxides, employing 20 to 80% byweight of monomers based on the grafting component in the graftcopolymerization. A mixture of maleic acid and acrylic acid in the ratiofrom 90:10 to 10:90 by weight is preferably employed for the grafting.

Polyglyoxylic acids suitable as component (B) are described, forexample, in EP-B 0 001 004, U.S. Pat. No. 5,399,286, DE-A 41 06 355 adEP-A 0 656 914. The endgroups of the polyglyoxylic acids may havedifferent structures.

Polyamidocarboxylic acids and modified polyamidocarboxylic acidssuitable as component (B) are disclosed, for example, in EP-A 0 454 126,EP-B 0 511 037, WO-A 94/01486 and EP-A 0 581 452.

Also particularly used as component (B) are polyaspartic acids orcocondensates of aspartic acid with other amino acids, C₄-C₂₅-mono- or-dicarboxylic acids and/or C₄-C₂₅-mono- or diamines. Particularlypreferably employed are polyaspartic acids prepared inphosphorus-containing acids and modified with C₆-C₂₂-mono- ordicarboxylic acids or with C₆-C₂₂-mono or diamines.

Condensates of citric acid with hydroxy carboxylic acids or polyhydroxycompounds suitable as component (B) are disclosed, for example, in WO-A93/22362 and WO-A 92/16493. Carboxyl-containing condensates of this typenormally have molecular weights of up to 10,000, preferably up to 5000.

Also suitable as component (B) are ethylenediaminedisuccinic acid,oxydisuccinic acid, aminopolycarboxylates, aminopolyalkylenephosphonatesand polyglutamates.

Oxidized starches can also be used as organic cobuilders in addition tocomponent (B).

Surfactants

Suitable anionic surfactants (C) are, for example, fatty alcoholsulfites of fatty alcohols with 8 to 22, preferably 10 to 18, carbonatoms, eg. C₉-C₁₁-alcohol sulfates, C₁₂-C₁₄-alcohol sulfates, cetylsulfate, myistyl sulfate, palmityl sulfate, stearyl sulfate and tallowfatty alcohol sulfate.

Other suitable anionic surfactants are sulfated ethoxylatedC₈-C₂₂-alcohols (alkyl ether sulfates) and their soluble salts.Compounds of this type are prepared, for example, by initiallyalkoxylating a C₈-C₂₂, preferably a C₁₀-C₁₁, alcohol eg. a fattyalcohol, and subsequently sulfating the alkoxylation product. Ethyleneoxide is preferably used for the alkoxylation, in which case 2 to 50,preferably 3 to 20, mol of ethylene oxide are employed per mole ofalcohol. However, the alcohols can also be alkoxylated with propyleneoxide, alone or with butylene oxide. Also suitable are those alkoxylatedC₈-C₂₂-alcohols which contain ethylene oxide and propylene oxide orethylene oxide and butylene oxide or ethylene oxide and propylene oxideand butylene oxide. The alkoxy-related C₈-C₂₂-alcohols may contain theethylene oxide, propylene oxide and butylene oxide units in the form ofblocks or in random distribution. Alkyl ether sulfates with a wide ornarrow alkylene oxide distribution can be obtained depending on thenature of the alkoxylation catalyst.

Other suitable anionic surfactants are alkanesulfonates such as C₈-C₂₄,preferably C₁₀-C₁₈, alkanesulfonates, and soaps such as the Na and Ksalts of C₈-C₂₄-carboxylic acids.

Further suitable anionic surfactants are linearC₉-C₂₀alkylbenzenesulfonates (LAS) and -alkyltoluenesulfonates.

Also suitable as anionic surfactants (C) are C₈-C₂₄-olefinsulfonates and-disulfonates which may also represent mixtures of alkene—andhydroxyalkanesulfonates and—disulfonates, alkyl ester sulfonates,sulfonated polycarboxylic acids, alkylglycerol sulfonates, fatty acidglycerol ester sulfonates, alkylphenol polyglycol ether sulfates,paraffinsulfonates with about 20 to about 50 carbon atoms (based onparaffin or paraffin mixtures obtained from natural sources), alkylphosphates, acylisethionates, acyltaurates, acylmethvitaurates,alkylsuccinic acids, alkenylsuccinic acids or their monoesters ormonoamides, alkylsulfosuccinic acids or their amides, mono- and diestersof sulfosuccinic acids, acylsarcosinates, sulfated alkyl polyglucosides,alkylpolyglycol carboxylates and hydroxyalkylsarcosinates.

The anionic surfactants are added to the detergents preferably in theform of salts. Suitable cations in the salts are alkali metal ions suchas sodium, potassium, lithium and ammonium ions, eg.hydroxyethylammonium, di(hydroxyethyl)ammonium andtri(hydroxyethyl)ammonium ions.

Component (C) is preferably present in the textile detergent formulationaccording to the invention in an amount of from 3 to 30% by weight, inparticular 5 to 15% by weight. If linear C₉-C₂₀-alkylbenzinesulfonatesLAS) are present, these are normally used in an amount of up to 10% byweight, in particular up to 8% by weight. It is possible to employ onlyone class of anionic surfactants alone, for example only fatty alcoholsulfates or only alkylbenzenesulfonates, but mixtures of various classescan also be used, eg. a mixture of fatty alcohol sulfates andalkylbenzenesulfonates. Mixtures of different species within individualclasses of anionic surfactants may also be employed.

Examples of suitable nonionic surfactants (D) are alkoxylatedC₈-C₂₂-alcohols such as fatty alcohol alkoxylates oroxoalcoholalkoxylates. The alkoxylation can be carried out with ethyleneoxide, propylene oxide and/or butylene oxide. Surfactants which can beemployed in this case are all alkoxylated alcohols which contain atleast two molecules of an abovementioned alkylene oxide in the adduct.Once again, block copolymers of ethylene oxide, propylene oxide and/orbutylene oxide are suitable, or adducts which contain said alkyleneoxides in random distribution. From 2 to 50, preferably 3 to 20, mol ofat least one alkylene oxide are used per mole of alcohol. Ethylene oxideis preferably employed as alkylene oxide. The alcohols preferably have10 to 18 carbon atoms. Alkoxylates with a wide or narrow alkylene oxidedistribution can be obtained depending on the nature of the alkoxylationcatalyst.

Another class of suitable nonionic surfactants comprises alkylphenolalkoxylates such as alkylphenol ethoxylates with C₆-C₁₄-alkyl chains and5 to 30 mol of alkylene oxide units.

Another class of nonionic surfactants comprises alkyl polyglucosides orhydroxyalkyl polyglucosides with 8 to 22, preferably 10 to 18, carbonatoms in the alkyl chain. These compounds usually contain 1 to 20,preferably 1.1 to 5, glucoside units.

Another class of nonionic surfactants comprises N-alkylglucamides withC₆-C₂₂-alkyl chains. Compounds of this type are obtained, for example,by acylation of reductively aminated sugars with appropriate long-chaincarboxylic acid derivatives.

Also suitable as nonionic surfactants (D) are block copolymers ofethylene oxide, propylene oxide and/or butylene oxide (Pluronic® andTetronic® brands of BASF AG), polyhydroxy or polyalkoxy fatty acidderivatives such as polyhydroxy fatty amides, N-alkoxy orN-aryloxy-polyhydroxy fatty amides, fatty amide ethoxylates, especiallyendgroup-capped and fatty alkanolamide alkoxylates.

Component (D) is preferably present in the textile detergent formulationaccording to the invention in an amount of from 1 to 20% by weight, inparticular 3 to 12% by weight. It is possible to employ only one classof nonionic surfactants, in particular only alkoxylated C₈-C₂₂-alcohols,but mixtures of various classes can also be used. Mixtures of differentspecies within the individual classes of nonionic surfactants can alsobe employed.

Since the balance between the types of surfactants mentioned is ofsignificance for the activity of the detergent formulation according tothe invention, the ratio by weight of anionic surfactants (C) tononionic surfactants (D) is preferably from 95:5 to 20:80, in particularfrom 70:30 to 50:50.

The detergents according to the invention can furthermore also containcationic surfactants (E).

Examples of suitable cationic surfactants are surface-active compoundscontaining ammonium groups, such as alkyldimethylammonium halides andcompounds of the formula

RR¹R²R³N⁺X⁺

where the radicals R to R³ are alcyl, aryl, aikylalkoxy, arylalkoxy,hydroxyalkyl(alkoxy), hydroxyaryl(alkoxy) groups and X is a suitableanion.

The detergents according to the invention may also contain ampholyticsurfactants (F), such as aliphatic derivatives of secondary or tertiaryamines which contain in one of the side chains an anionic group,alkyldimethylamine oxides or alkyl- or alkoxymethylamine oxides.

Components (E) and (F) may comprise up to 25%, preferably 3-15%, in thedetergent formulation.

Bleaches

In another preferred embodiment, the textile detergent formulationaccording to the invention additionally contains 0.5to 30% by weight, inparticular 5 to 27% by weight, especially 10 to 23% by weight, of bleach(G). Examples are alkali metal perborates or alkali metal carbonateperhydrates, especially the sodium salts.

One example of an organic peracid which can be used is peracetic acid,which is preferably used in commercial textile laundry or commercialcleaning.

Bleach or textile detergent compositions which can advantageously beused contain C₁₋₁₂-percarboxylic acids, C₈₋₁₆-dipercarboxylic acids,imidopercaproic acids, or aryldipercaproic acids. Preferred examples ofacids which can be used are peracetic acid, linear or branchedperoctanoic, -nonanoic, -decanoic or dodecanoic acids, diperdecanedioicand -dodecanedioic acids, mono- and diperphthalic acids, -isophthalicacids and -terephthalic acids, phthalimidopercaproic acid andterephthaloyldipercaproic acid. It is likewise possible to use polymericperacids, for example those containing acrylic acid basic units in whicha peroxy functionality is present. The percarboxylic acids can be usedas free acids or as salts of the acids, preferably alkali metal oralkaline earth metal salts. These bleaches (G) may be used incombination with from 0 to 15% by weight, preferably 0.1 to 15% byweight, in particular 0.5 to 8% by weight, of bleach activators (H). Thebleach (G) is (if present) employed in color detergents as a rulewithout bleach activator (H), otherwise bleach activators (H) are alsousually present.

Suitable bleach activators (H) are:

polyacylated sugars, eg. pentaacetylglucose;

acyloxybenzenesulfonic acids and their alkali metal and alkaline earthmetal salts, eg. sodium p-isononanoyloxybenzenesulfonate or sodiump-benzoyloxy-benzenesulfonate;

N,N-diacylated and N,N,N′,N′-tetraacylated amines, eg.N,N,N′,N′-tetraacetylmethylenediamine and ethylenediamine (TAED),N,N-diacetylamline, N,N,-diacetyl-p-toluidine or 1,3-diacylatedhydantoins such as 1,3-diacetyl-5,5-dimethylhydantoin;

N-alkyl-N-sulfonylcarboxamides, eg. N-methyl-N-mesylacetamide orN-methyl-N-mesylbenzamide;

N-acylated cyclic hydrazides, acylated triazoles or urazoles, eg.monoacetylated maleic hydrazides;

O,N,N-trisubstituted hydroxylamines, eg.O-benzoyl-N,N-succinylhydroxylamine, orO-acetyl-N,N-succinylhydroxylamine or O,N,N-triacetylhydroxylamine,

N,N-diacylsulfamides, eg. N,N′-dimethyl-N,N′-diacetylsulfamide orN,N′-diethyl-N,N′-dipropionylsulfamide;

triacylcyanurates, eg. triacetylcyanurate or tribenzoylcyanurate;

carboxylic anhydrides, eg. benzoic anhydride,

m-chlorobenzoic anhydride or phthalic anhydride;

1,3-diacyl-4,5-diacyloxyimidazolines, eg.1,3-diacetyl-4,5-diacetoxyimid-azoline;

tetraacetylglycoluril and tetrapropionylglycoluril;

diacylated 2,5-diketopiperazines, eg. 1,4-diacetyl-2,5-diketopiperazine,

products of the acylation of propylenediurea and2.2-dimethylpropylenediurea, eg. tetraacetylpropylenediurea;

α-acyloxypolyacyitalonanides, eg. α-acetoxy-N,N′diacetylmalonamide;

diacyldioxohexahydro-1,3,5-triazines, eg.1,5-diacetyl-2,4-dioxohexahydro-1,3,5-triazine;

benzo(4H)-1,3-oxazin-4-ones with alkyl radicals, eg. methyl, or aromaticradicals, eg. phenyl, in position 2.

The described bleach system consisting of bleach and bleach activatorsmay also contain bleach catalysts. Examples of suitable bleach catalystsare quaternized imines and sulfone imines which are described, forexample, in U.S. Pat. No. 5,360,569 and EP-A 0 453 003. Particularlyeffective bleach catalysts are manganese complexes which are described,for example, in WO-A 94/21777. Compounds of this type are, if they areused, incorporated into the detergent formulations in amounts notexceeding 1.5% by weight, in particular up to 0.5% by weight. Bleachcatalysts which can likewise be used are the amines described in theapplication filed at the same time as this application and entitled“Bleach boosters for bleach and textile detergent compositions”.

Besides the described bleach system consisting of bleaches and bleachactivators with or without bleach catalysts, the use of systems withenzymatic release of peroxide or of photoactivated bleach systems forthe textile detergent formulation according to the invention is alsoconceivable.

Enzymes

In another preferred embodiment, the textile detergent formulationaccording to the invention additionally contains 0.05 to 4% by weight ofenzymes (J). Enzymes which are preferably employed in detergents areproteases, amylases, lipases and cellulases. The amounts of enzymesadded are preferably 0.1-1.5% by weight, in particular preferably 0.2 to1.0% by weight, of the formulated enzyme. Examples of suitable proteasesare Savinase and Esperase (manufactured by Novo Nordisk). An example ofa suitable lipase is Lipolase (manufactured by Novo Nordisk). An exampleof a suitable cellulase is Celuzym (manufactured by Novo Nordisk). It isalso possible to use peroxidases to activate the bleach system. Singleenzymes or a combination of different enzymes can be employed. Thetextile detergent formulation may also contain enzyme stabilizers, eg.calcium propionate, sodium formate or boric acids or their salts, and/oroxidation inhibitors.

Other Ingredients

The textile detergent formulation according to the invention may,besides the main components (A) to (J) mentioned, also contain thefollowing other conventional additives in the amounts customary for thispurpose:

aritiredeposition agents and other soil release polymers

Suitable other soil release polymers and/or antiredeposition agents fordetergents are, for example:

polyesters from polyethylene oxides with ethylene glycol and/orpropylene glycol and aromatic dicarboxylic acids or aromatic andaliphatic dicarboxylic its acids;

polyesters from polyethylene oxides endgroup-capped at one end withdihydric and/or polyhydric alcohols and dicarboxylic acid.

Polyesters of this type are disclosed, for example, in U.S. Pat. No.3,557,039, GB-A 1 154 730, EP-A-0 185 427, EP-A-0 241 984, EP-A0 241985, EP-A-0 272 033 and U.S. Pat. No. 5,142,020.

Other suitable soil release polymers are amphiphilic graft or othercopolymers of vinyl and/or acrylic esters on polyalkylene oxides (cf.U.S. Pat. No. 4,746,456, U.S. Pat. No. 4,846,995, DE-A-37 11 299, U.S.Pat. No. 4,904,408, U.S. Pat. No. 4,846,994 and U.S. Pat. No.4,849,126), or modified celluloses such as methylcellulose,hydroxypropylcellulose or carboxymethylcellulose.

Color transfer inhibitors, for example homo- and copolymers ofvinylpyrrolidone, of vinylimidazole, of vinyloxazolidone or of4-vinylpyridine N-oxide with molecular weights of from 15,000 to100,000, and crosslinked fine-particle polymers based on these monomers;

non-surfactant foam suppressants or foam inhibitors, for exampleorganopolysiloxanes and their mixtures with microfine, possiblysilanized silica, and paraffins, waxes, microcrystalline waxes and theirmixtures with silanized silica;

complexing agents (also acting as organic cobuilders);

optical brighteners;

polyethylene glycols;

perfumes or fragrances;

bulking agents;

inorganic fillers, eg. sodium sulfate;

formulation aids;

solubility improvers;

opacifying and pearlescent agents;

dyes;

corrosion inhibitors;

peroxide stabilizers;

electrolytes.

The detergent formulation according to the invention is solid, ie. isnormally in the form of a powder or granules, or an extrudate or tablet.

The powder or granular detergents according to the invention may containup to 60% by weight of inorganic fillers. Sodium sulfate is normallyused for this purpose. However, the detergents according to theinvention preferably contain only up to 20% by weight, particularlypreferably only up to 8% by weight, of fillers, especially in the caseof compact or ultracompact detergents. The solid detergents according tothe invention may have bulk densities varying in the range from 300 to1300 g/l, in particular from 550 to 120 g/l. Modern compact detergentsusually have high bulk densities and a granular structure. The processescustomary in the industry can be employed for the required compaction ofthe detergents.

The detergent formulation according to the invention is produced and,where appropriate, formulated by conventional methods.

Typical compositions of compact heavy duty detergents and colordetergents are indicated below (the percentage data hereinafter and inthe examples are based on weight; the data in parentheses for thecompositions are preferred ranges):

Composition of compact heavy duty detergents (powder or granule form)1-60% (8-30%) of at least one anionic (C) and one nonionic surfactant(D) 5-50% (10-45%) of at least one inorganic builder (A) 0.1-20%(0.5-15%) of at least one organic cobuilder (B) 5-30% (10-25%) of aninorganic bleach (G) 0.1-15% (1-8%) of a bleach activator (G) 0-1% (max.0.5%) of a bleach catalyst 0.05-5% (0.2-2.5%) of a color transferinhibitor 0.3-1.5% of a soil release agent according to the invention0.1-4% (0.2-2%) of enzyme or enzyme mixture (H) Other conventionaladditives: sodium sulfate, complexing agents, phosphonates, opticalbrighteners, perfume oils, foam suppressants, antirepostion agents,bleach stabilizers

Composition of color detergents (powder or granule form) 3-50% (8-30%)of at least one anionic (C) and one nonionic surfactant (D) 10-60%(20-55%) of at least one inorganic builder (A) 0-15% (0-5%) of aninorganic bleach (G) 0.05%-5% (0.2-2.5%) of a color transfer inhibitor0.1-20% (1-8%) of at least one organic cobuilder (B) 0.2-2% of enzyme orenzyme mixture (J) 0.2-1.5% of soil release agent according to theinvention Other conventional additives: sodium sulfate, complexingagents, phosphonates, optical brighteners, perfume oils, foamsuppressants, antirepostion agents, bleach stabilizers.

The crosslinked nitrogenous compounds according to the invention (soilrelease agents) are present in detergents according to the invention inamounts of from 0.05 to 5% by weight, preferably 0.1 to 4% by weight, inparticular 0.2 to 2% by weight.

The invention is explained in detail by means of the following examples.

EXAMPLES General Method 1

Crosslinking of Polyethyleneimine or Polyethyleneimine Derivatives withthe Bisglycidyl Ether of a Polyethylene Glycol of Molecular Weight 1500

A 20 to 22% strength aqueous solution of a polyethylene glycolbisglycydyl ether of average molecular weight 1600 (or itsbischlorohydrin) is added in portions to a 25% strength aqueous solutionof the polyethyleneimine or derivative at 70° C. until the reactionsolution has a viscosity of about 500 to 1000 mpas. The pH of thesolution is adjusted to 7.5 to 8.0 with 85% strength formic acid.

This general method can be applied, for example, to polyethyleneiminesand their amidation products.

Example A

Polyethyleneimine from 10 mol of Ethyleneimine Crosslinked withBisglycidylether of a Polyethylene Glycol of Molecular Weight 1500

A 60% strength ethyleneimine solution composed of 43 g (1 mol) ofethyleneimine and 29 g of ice is added dropwise to a catalyst solutioncomposed of 6.0 g. (0.10 mol) of ethylenediamine, 2.2 g (0.05 mol) ofCO₂ and 17 g of deionized water at 90° C. The mixture is then stirred at90° C. until the Preuβmann test* for alkylating substances is negative.The product obtained in this way is crosslinked with the bisglycidylether by general method 1.

Example B

Polyethyleneimine from 20 mol of Ethyleneimine Crosslinked withBisglycidylether of a Polyethylene Glycol of Molecular Weight 1500

A 60% strength ethyleneiniine solution composed of 43 g (1 mol) ofethyleneimine and 29 g of ice is added dropwise to a catalyst solutioncomposed of 3.0 g (0.05 mol) of ethylenediamine, 1.1 g (0.025 mol) ofCO₂ and 17 g of deionized water at 90° C. The mixture is then stirred at90° C. until the Preuβmann test* for alkylating substances is negative.The product obtained in this way is crosslinked with the bisglycidylether by general method 1.

Example C

Amidation of Polyethyleneimine with Benzoic Acid 20:1, Crosslinked withBisglycidyl Ether of a Polyethylene Glycol of Molecular Weight 1500

183.18 g of benzoic acid (1.5 mol) are introduced in portions into 1290g of anhydrous Polyethyleneimine (=30 Eq N), prepared as in Example A,under nitrogen at 140° C. The mixture is then stirred at 180° C. untilthe acid number is less than 5% of the initial value. The productobtained in this way is crosslinked with the bisglycidyl ether bygeneral method 1.

Example D

Amidation of Polyethyleneimine with Benzoic Acid 10:1, Crosslinked withBisglycidyl Ether of a Polyethylene Glycol of Molecular Weight 1500

183.2 g of benzoic acid (1.5 mol) are introduced in portions into 645 gof anhydrous polyethyleneimine (=15 Eq N), prepared as in Example B,under nitrogen at 140° C. The reaction temperature is raised to 180° C.,and the water formed in the reaction is distilled out under a gentlestream of nitrogen until the acid number is less than 5% of the initialvalue. The product obtained in this way is crosslinked with thebisglycidyl ether by general method 1.

General Method 2

Crosslinking of Tetraaminopropylethylenediamine and Derivatives withBisglycidyl Ether of a Polyethylene Glycol of Molecular Weight 1500

An approximately 2% strength aqueous solution of a polyethylene glycolbisglycidyl ether of molecular weight 1600 (or its bischlorohydrin) isadded in portions to a 25% strength aqueous solution oftetraaminopropylethylenediamine at 70° C. until the reaction solutionhas a viscosity of about 500 to 1000 mPas. If the pH falls below 9, NaOH(5% strength) is added in portions until the pH reaches 10.5.

This method can be used for tetraaminopropylethylenediamine, its higherhomologs and for their amidation products with various degrees ofamidation.

Example E

N,N,N′,N′-Tetraaminopropyl-1,2-ethylenediamine (N6 Amine), Crosslinkedwith Bisglycidyl Ether of a Polyethylene Glycol of Molecular Weight 1500

Preparation of N,N,N′,N′-tetracyanoethyl-1,2-ethylenediamine: 443 g(8.35 mol) of acrylonitrile are added over the course of 90 minutes to asolution of 100 g (1.67 mol) of 1,2-ethylenediamine in 1176 ml of water.The temperature must not exceed 40° C. during this. After the additionof the acrylonitrile is complete, the flask is stirred for 1 hour at 40°C. and for two further hours at 80° C. Excess acrylonitrile issubsequently distilled off, and then most of the water is distilled offby applying a water pump or oil pump vacuum. The tetracyanoethylatedethylenediamine is recrystallized from methanol and filtered off withsuction. The yield is 478 g (1.58 mol).

Preparation of N,N,N′,N′-tetraaminopropyl-1,2-ethylenediamine N6 amine):400 ml/h of a mixture of 20% by weightN,N,N′,N′-tetracyanoethyl-1,2-ethylenediamine and 8% by weightN-methylpyrrolidone and 3500 ml/h of ammonia are passed over 4 1 of afixed bed catalyst of composition 90% by weight CoO, 5% by weight MnO,5% by weight P₂O₅ in a 5 1 fixed bed reactor at 130° C. under a pressureof 200 bar of hydrogen. Removal of the N-methylpyrrolidone under reducedpressure and fractional distillation (boiling point: 218° C. under 6mbar) result in N,N,N′,N′-tetra-aminopropyl-1,2-ethylenediamine (N6amine) in 95% yield. The product was checked for purity and completenessof the reaction by ¹³C and ¹H NMR and mass spectroscopy.

The product obtained in this way is crosslinked with the bisglycidylether by general method 2.

(* Preuβmann test=test for alkylating compounds, procedure described byJ. Epstein et al., Analyt. Chem. 27 (1955) 1435 and R. Preuβmann et al.,Arzneimittelforsch. 19 (1969) 1059.)

Washing Tests

The soil release effect of the compounds according to the invention wasdetermined in washing tests in a Launder-O-meter under standardizedconditions. The detergent formulation (composition I in Table 4) wasused for the tests. Use of detergent formulations II to XI is likewisepossible according to the invention.

Detergent formulation I was initially investigated without a compoundaccording to the invention and subsequently with the compounds accordingto the invention from Examples A to E in concentrations of 2% of thetotal weight of detergent. The test fabrics were prewashed three timeswith detergent formulation I with these additives (prewash; washingconditions hereinafter), dried and stained with 0.2 g of used engineoil. The oil spots were left to age for 14 hours. The test fabrics werethen washed a with detergent formulation I with additives (main wash),and the soil detachment was determined.

Washing conditions Machine: Launder-O-meter from Atlas, Chicago Washliquor: 250 ml Washing time: 30 min at 60° C. Detergent dose:  6 g/lWater hardness:  3 mmol; Ca:Mg 4:1 Liquor ratio: 1:12.5 Test fabrics:Cotton 221, PES850, PES/cotton 65:53 blended fabric

Washing Result

To determine the washing result, the reflectances were determined forthe test fabric before washing (R_(o)), for the stained test fabricbefore the main wash (R before) and after the main wash (R after). Thepercentage soil release was then determined using

% soil release=R after−R before)/(Ro−R before)×100

A higher percentage soil release means better removal of the spot.Complete removal of the spot corresponds to 100%. The crucial point inthis connection is the difference in % soil release between thedetergent formulation without and with the compound according to theinvention. A greater difference between % soil release without and withcompound according to the invention means a greater improvement in thewashing result with the detergent formulation on addition of thecompound according to the invention. The results of the washing testsare indicated in Tables 1 and 2.

TABLE 1 Improvement in the soil detachment by addition of 2% of thecompounds according to the invention Fabric: Polyester PES 850 Example Rbefore R after Difference % Soil release without 23.6 50.5 26.9 45.3 A24.1 64.4 40.3 68.5 B 25.4 65.8 40.4 70.3 C 24.7 96.2 44.5 76.4 D 24.667.7 43.1 73.8 E 25.1 64.5 39.4 68.2

TABLE 2 Difference between single wash cycle performance and soilrelease effect Fabric: Polyester PES 850 R R % Soil % SR with ExampleMode before after Release − % SR without* A with/without 22.4 55 53.813.2 without/with 23.8 44.5 34.9 −5.7 D with/without 23.7 63.7 67.4 26.8without/with 23.8 46.4 38.2 −2.4 E with/without 23.9 60.2 61.4 20.8without/with 23.8 47.2 39.5 −1.1 *% SR without = 40.6

It is evident from Tables 1 and 2 that the compounds according to theinvention of Examples A to E distinctly improve soil detachment duringwashing. The degree of whiteness of the fabric after washing, R after,is significantly improved by adding the compounds according to theinvention.

The results indicated in Table 2 make it clear that the improved soildetachment is a soil release effect and not a pure single wash cycleeffect. In the series of tests on which this test was based, twodifferent application variants were carried out:

Mode 1: three prewashes with detergent with additive, main wash (afterstaining) without additive in the detergent (=with/without)

Mode 2: three prewashes without additive in the detergent, main wash(after staining) with detergent with additive (=without/with)

If, in Mode 1, there is an improvement in soil detachment compared withthe test with prewash and main wash with detergent but without additive(% SR without), a soil release effect is achieved. If, in Mode 2, thereis an improved soil detachment, a single wash cycle effect is achieved.It is evident from the results in Table 2 that improved soil detachmentcan be achieved only in Mode 1, so that the effect achieved by theproducts according to the invention derives from a soil release action.

The crosslinked polyamines were also employed in combination withcorresponding but uncrosslinked polyamines. The results are shown inTable 3.

TABLE 3 Improvement in soil detachment on addition of combinations ofuncrosslinked and crosslinked polyamines In each case 2 + 2% testsubstance Cotton Blended fabric Polyester Example R before R after % SRR before R after % SR R before R after % SR without 22.7 63 69.4 25.460.1 60.3 19.2 41.9 35.9 A + A′ 21.6 65.9 74.4 21.9 64.5 96.8 16.4 55.258.9 C + C′ 21.8 67.8 77.9 24.8 70.9 79.3 18.3 62 68.4 E + E′ 21.7 68.378.7 24.3 70.8 79.3 19.3 56.3 59.2 C + OA 21.9 77.3 94 21.7 71.2 80.819.4 74 86.9 A′ = Example A, uncrosslinked C′ = Example C, uncrosslinkedE′ = Example E, uncrosslinked OA = octylamine

It is evident from the results shown in Table 3 that mixtures ofcrosslinked and uncrosslinked polyamines can be employed advantageouslyfor washing all common textiles such as cotton polyester and fabricsblended from cotton and polyester.

TABLE 4 Composition of detergent formulations Composition in %Ingredients I II III IV V VI VII VIII IX X XI XII LinearC₁₂-alkylbenzenesulfonate 9 11 11 11 (Na salt) C₁₂-C₁₈-alkyl sulfate 1.59 1 1 8 8 10 10 10 8 C₁₂ Fatty alcohol × 2EO sulfate 2 Oleylsarcosine Nasalt 9 C₁₂-C₁₈ Fatty alcohol × 4EO 3 C₁₂-C₁₈ Fatty alcohol × 7EO 7 7 7C₁₃-C₁₅ Oxo alcohol × 7EO 7 6 6 6 8 C₁₆-C₁₈-Glucamide 4 C₁₂-C₁₄-Alkylpolyglucoside 9 9 C₈-C₁₈-Fatty acid 9 methyltetraglycolamide Soap 2 2 22 2 1 1 1 1 1 1 2 Na metasilicate × 5.5H₂O 3 3 3 3 Mg silicate 1 1 2 2 23 3 Na silicate 2 2 2 3 3 Zeolite A 45 45 40 40 40 36 20 30 30 30 30 20Zeolite P 10 Sheet silicate SKS6 15 Sodium carbonate 7 7 6 6 6 12 10 8 88 8 Sodium citrate 12 12 5 5 Sodium citrate × 2H₂O 18 18 18 MGDA tri-Na5 5 5 Phosphonate 1 1 2 TAED 4 4 4 4 4 4 5 Sodium perborate × 4H₂O 20Sodium perborate × 1H₂O 14.4 14.4 14.4 Sodium percarbonate 15 15 15Carboxymethylcellulose 1 1 1 1 1 1.5 1 1.2 1.2 1.2 1.2 1 Lipase 0.2 0.20.2 0.2 0.2 0.2 0.2 0.2 0.2 0.2 Protease 0.3 0.3 0.3 0.3 0.3 0.3 0.3 0.30.3 0.3 Cellulase 0.5 0.5 0.5 0.5 0.5 0.5 0.5 0.5 0.5 0.5 Sodium sulfate3 3 3 3 3 2 3 3 3 3 3 3 Polymer (AA/MA copolymer) 5 5 5 5 5 3 5 5 5 5 55 Soil release polymer 2 1 1 1 0.5 0.5 0.5 0.5 0.5 0.5 0.5 Colortransfer inhibitor 1.5 1 1 1 0.5 Water to 100 to 100 to 100 to 100 to100 to 100 to 100 to 100 to 100 to 100 to 100 to 100

Enzyme-stabilizing Action

To test the enzyme-stabilizing action of the compounds according to theinvention, they were incorporated into a liquid detergent formulation,and a protease was added to the latter. After 25 and 50 days, washingtests were carried out with soiled test fabric. Detergent formulationswithout added enzyme and with added enzyme but without addition of thecompounds according to the invention were used for comparison.

The washing tests were evaluated by measuring the color strength of thetest fabrics and determining the single wash cycle effect A_(sba) fromthe color strength by the method described in A Kud, Seifen, Öle, Fette,Wachse, 119 (1993), 590-594.

Test conditions Storage: Storage temperature for the 30° C. liquiddetergent formulation: Enzyme: Protease, Savinase ® 16L (manufactured byNovo Nordisk) Amount of enzyme 0.4% Savinase 16L Storage time: 50 daysWashing conditions: Machine: Launder-O-meter Soiled fabric: 2.5 g of CFTAS 10 (Pigment/oil/milk) Ballast fabric: 5.0 g of cotton Detergent:Formulation XII hereinafter Amount: 4.0 g/l Amount of liquor: 250 gWashing temperature: 20° C. Water hardness: 3 mmol/l Ca/Mg ratio:4.0:1.0 Washing time: 15 min Detergent formulation XII: Linearalkylbenzenesulfonate 19.5 Coconut fatty acid  8.3 C₁₃/₁₅ oxo alcoholethoxylate 16.8 Ethanol  0.7 1,2-Propanediol 11.0 Ethanolamine  9.4Citric acid  4.8 Sokolan ® CP5  0.9 Dequest ® 2006  1.0 (manufactured byMonsanto) Savinase ® 16L  0.4 (or 0 in the comparative test withoutenzyme) Polymer according to the invention  2.5 (or 0 in the comparativetest without polymer)

The results are listed in Table 5 hereinafter.

TABLE 5 Results of tests on enzyme stabilization Single Amount Amountwash cycle Storage of enzyme of polymer effect A_(ohm) Test [days] [%]Polymer [%] [%] 1 25 — — — 38 2 25 0.4 — — 55 3 25 — C 2.5 37 4 25 0.4 C2.5 66 5 50 — — — 41 6 50 0.4 — — 46 7 50 0.4 C 2.5 68

The polymer from Example C was used as polymer. The results in Table 5show that a distinctly improved enzyme activity on prolonged storage isachieved with the crosslinked compounds according to the invention bycomparison with the tests without added polymer. After storage of theliquid detergent without compound according to the invention at 30° C.for 50 days, the protease action has been almost completely lost,whereas there is still a high protease activity in the formulations withcompound C after 50 days.

We claim:
 1. A water-soluble cross inked product obtainable bycrosslinking amines of the formula (II) (R¹R¹)N—X—N(R¹R¹)  (II) wherethe radicals R¹ are (R²R²)N—(CH₂)_(n) radicals, the radicals are R² arehydrogen atoms or (R³R³)N—(CH₂)_(n)— radicals, the radicals R³ arehydrogen atoms or (R⁴R⁴)N—(CH₂)_(n)— radicals, the radicals R⁴ arehydrogen atoms or (R⁵R⁵)N—(CH₂)_(n)— radicals, the radicals R⁵ arehydrogen atoms or (R⁶R⁶)N—(CH₂)_(n)— radicals, the radicals R⁶ arehydrogen atoms, n is 2, 3 or 4, and the radical X is one of the radicals

—(CH₂)_(p)—, —(CH₂)₃—NR¹¹—(CH₂)₃—,—(CH₂)₁—{O—(CH₂)_(k)}_(m)—O—(CH₂)₁—C₂₋₂₀-alkylene, the radical Y is anoxygen atom, a CR⁷R⁹C═O or SO₂ radical, p is an integer from 2-20, l andk are, independently of one another, an integer from 2-6, m is aninteger from 1-40, the radicals R⁷, R⁸, R⁹ and R¹⁰ are, independently ofone another, hydrogen atoms or C₁₋₆-alkyl radicals, and the radical R¹¹is C₁₋₂₀-alkyl, C₂₋₂₀-dialkylamino-C₂₋₁₀-alkyl,C₁₋₁₀-alkoxy-C₂₋₁₀-alkyl, C₂₋₂₀-hydroxyalkyl, C₃₋₁₂-cycloalkyl,C₄₋₂₀-cycloalkylalkyl, C₂₋₃₀-alkenyl, C₄₋₃₀-dialkylaminoalkenyl,C₃₋₃₀-alkoxyalkenyl, C₃₋₂₀-hydroxyalkenyl, C₅₋₂₀-cycloallcylalkenyl, anaryl or a C₇₋₂₀-arykalkyl radical which is unsubstituted or substitutedone to five times by C₁₋₈-alkyl, C₂₋₈-dialkylamino, C₁₋₈-alkoxy,hydroxyl, C₃₋₈-cycloalkyl and/or C₄₋₁₂-cycloalkylalkyl, or two radicalsR¹¹ together form an alkylene chain which may be interrupted by nitrogenor oxygen, such as from ethylene oxide, propylene oxide, butylene oxideand —CH₂—CH(CH₃)—O— or polyisobutylene with 1 to 100 isobutylene units,with at least one bifunctional crosslinker (b) which reacts with NHgroups.
 2. A water-soluble crosslinked product of claim 1, in which theamine of general formula (II) is N,N,N′,N′-tetraaminopropyl-1,2-ethylenediamine.
 3. The product as claimed in claim 1, wherein the crosslinker(b) is selected from the group consisting of the halogen-freecrosslinkers: (1) polyepoxides, (2) ethylene carbonate, propylenecarbonate and/or urea, (3) monoethylenically unsaturated carboxylicacids and their esters, amides and anhydrides, at least dibasiccarboxylic acids or polycarboxylic acids, and their esters, amides andanhydrides, (4) products of the reaction of polyetherdiamines,alkylenediamines, polyalkylenepolyamines, bifunctional ormultifunctional alcohols, alkylene gylcols, polyalkylene glycols,functionalized polyesters or polyamides or their mixtures withmonoethylenically unsaturated carboxylic acids or their esters, amidesor anhydrides, the reaction products having at least two ethylenicdouble bonds, carboxamide, carboxyl or ester groups as functionalgroups, (5) products, containing at least two aziridino groups, of thereaction of dicarboxylic esters with ethyleneimine, (6) cumulenes andpolyheterocumulenes, (7) β-keto esters, β-keto acids and β-ketoaldehydes, (8) functionalized glycidyl ethers; the halogen-containingcrosslinkers: (9) polyhalides, (10) glycidyl halides, (11)chloroformates and chloroacetic acid derivatives, (12) epichlorohydrin,glycerol chlorohydrin, polyether dichlorohydrin compounds, (13)phosgene; and mixtures thereof.
 4. The product as claimed in claim 1,wherein the crosslinker (b) is a bisglycidyl ether of a polyethyleneglycol with a weight average molecular weight of from 300 to
 3000. 5. Adetergent or cleaner comprising the product as defined in claim 1, andat least one surfactant.
 6. The detergent or cleaner as claimed in claim4, further comprising at least one enzyme.